Advanced Green Composites
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Anil N. Netravali is the Jean and Douglas McLean Professor of Fiber Science and Apparel Design in the Department of Fiber Science and Apparel Design at Cornell University. Since 1984 he has been working in the field of polymer composites. He has published widely in the area of fiber/resin interface characterization and control through fiber surface modification and resin modification using nanoparticles and nanofibrils. In the past 25 years he has made significant contributions in the area of 'green' resins, composites and nanocomposites that are fully derived from plants. He was the recipient of the Fiber Society's Founders Award in 2012 and received the Green of the Crop award from the Creative Core (NY) in 2010.
Content
Preface xiii
1 Introduction 1 Anil N. Netravali
1.1 Introduction 2
2 Green Resins from Plant Sources and Strengthening Mechanisms 11 Muhammad M. Rahman and Anil N. Netravali
2.1 Introduction 12
2.2 Green Resins from Agro-Resources 14
2.2.1 Plant Protein-Based Resins 14
2.2.2 Plant Starch-Based Resins 21
2.3 Green Resins from Microbial Fermentation 25
2.3.1 Polyhydroxyalkanoates 25
2.3.2 Pullulan 27
2.4 Green Resins Using Monomers from Agricultural Resources 29
2.4.1 Polylactic Acid 29
2.5 Strengthening of Green Resins using Nano-Fillers 32
2.5.1 Inorganic Nano-Fillers 33
2.5.2 Organic Nano-Fillers 38
2.6 Conclusions 43
References 44
3 High Strength Cellulosic Fibers from Liquid Crystalline Solutions 57 Yuxiang Huang and Jonathan Y. Chen
3.1 Introduction 57
3.2 Fibers from Liquid Crystalline Solutions of Cellulose Derivatives 59
3.3 Fibers from Liquid Crystalline Solution of Nonderivatized Cellulose 60
3.4 Regenerated-Cellulose/CNT Composite Fibers with Ionic Liquids 61
3.5 Future Prospects 63
Summary 64
References 65
4 Cellulose Nanofibers: Electrospinning and Nanocellulose Self-Assemblies 67 You-Lo Hsieh
4.1 Introduction 68
4.2 Electrospinning of Cellulose Solutions 70
4.3 Cellulose Nanofibers via Electrospinning and Hydrolysis of Cellulose Acetate 70
4.4 Bicomponent Hybrid and Porous Cellulose Nanofibers 72
4.5 Wholly Polysaccharide Cellulose/Chitin/Chitosan Hybrid Nanofibers 74
4.6 Surface-Active Cellulose Nanofibers 76
4.7 Nanocelluloses 77
4.8 Nanocelluloses from Agricultural By-Products 79
4.9 Source Effects - CNCs from Grape Skin, Tomato Peel, Rice Straw, Cotton Linter 80
4.10 Process Effect - Nanocelluloses from Single Source (Corn Cob, Rice Straw) 82
4.11 Ultra-Fine Cellulose Fibers from Electrospinning and Self-Assembled Nanocellulose 85
4.12 Further Notes on Nanocellulose Applications and Nanocomposites 87
Acknowledgement 88
References 88
5 Advanced Green Composites with High Strength and Toughness 97 Anil N. Netravali
5.1 Introduction 98
5.2 'Greener' Composites 99
5.3 Fully 'Green' Composites 101
5.4 'Advanced Green Composites' 102
5.5 Conclusions 106
References 108
6 All-Cellulose (Cellulose-Cellulose) Green Composites 111 Shuji Fujisawa, Tsuguyuki Saito and Akira Isogai
6.1 Introduction 111
6.1.1 Cellulose 111
6.1.2 Nanocelluloses for Polymer Composite Materials 112
6.1.3 All-Cellulose Composites 114
6.2 Preparation of ACCs 114
6.2.1 Dissolution of Cellulose 114
6.2.1.1 Aqueous Solvents 114
6.2.1.2 Organic Solvents 115
6.2.1.3 Ionic Liquids 115
6.2.2 Preparation of ACCs 116
6.2.2.1 One-Phase Preparation 116
6.2.2.2 Two-Phase Preparation 116
6.3 Structures and Properties of ACCs 120
6.3.1 Optical Properties 120
6.3.2 Mechanical Properties 120
6.3.3 Thermal Expansion Behavior 124
6.3.4 Gas Barrier Properties 124
6.3.5 Biodegradability 125
6.4 Future Prospects 125
6.5 Summary 126
6.6 Acknowledgements 127
References 127
7 Self-Healing Green Polymers and Composites 135 Joo Ran Kim and Anil N. Netravali
7.1 Introduction 136
7.1.1 Self-Healing Property in Materials: What is it and Why it is Needed? 136
7.2 Types of Self-Healing Approaches Used in Thermoset Polymers 137
7.2.1 Microcapsule-Based Self-Healing System 138
7.2.1.1 Microencapsulation Techniques 139
7.2.1.2 Microcapsule Systems for Self-Healing 148
7.2.2 Vascular Self-Healing System 158
7.2.2.1 One-, Two-, or Three-Dimensional Microvascular Systems 159
7.2.3 Intrinsic Self-Healing System 161
7.2.3.1 Test Methods to Characterize Self-Healing 162
7.2.3.2 Quasi-Static Fracture Methods 163
7.2.3.3 Fatigue Fracture Methods 165
7.2.3.4 Impact Fracture Methods 166
7.2.3.5 Other Techniques 166
7.3 Self-Healing Polymers from Green Sources 167
7.3.1 Self-Healing Polymers in Biomaterials 168
7.3.2 Self-Healing Green Resins and Green Composites 170
7.4 Summary and Prospects 173
Acknowledgements 175
References 175
8 Transparent Green Composites 187 Antonio Norio Nakagaito, Yukiko Ishikura and Hitoshi Takagi
8.1 Introduction 187
8.2 Cellulose Nanofiber-Based Composites and Papers 189
8.2.1 Bacterial Cellulose-Based Composites 189
8.2.2 CNF-Based Composites 191
8.2.3 Transparent Nanopapers 194
8.2.4 All Cellulose Transparent Composites 195
8.3 Chitin-Based Transparent Composites 197
8.3.1 Chitin Nanofiber-Based Composites 197
8.3.2 Micro-Sized Chitin Composites 199
8.3.3 Chitin-Chitosan Transparent Green Composites 200
8.3.4 All Chitin Nanofiber Transparent Films 202
8.4 Electronic Devices Based on CNF Films and Composites 202
8.5 Future Prospects 205
8.6 Summary 206
References 206
9 Toughened Green Composites: Improving Impact Properties 211 Koichi Goda
9.1 Introduction 211
9.2 Significance of Fiber Length in Toughened Fibrous Composites 212
9.3 Impact Properties of Green Composites 217
9.3.1 Relation Between Interfacial and Mechanical Properties in Green Composites 217
9.3.2 A Pattern of Increase in Tensile Strength and Decrease in Impact Strength 221
9.3.3 Effect of Toughened Resin 227
9.3.4 Approaches to Increase Both TS and IS 228
9.4 Role of Large Elongation at Break in Regenerated Cellulose Fibers 229
9.5 Toughened Cellulose Fibers and Green Composites 231
9.5.1 Toughening Mechanism of Regenerated Cellulose Fibers 231
9.5.2 Mercerization Effect 234
9.5.3 Other Beneficial Chemical Treatments 238
9.6 Conclusions 240
Appendix 241
References 243
10 Cellulose Reinforced Green Foams 247 Jasmina Obradovic, Carl Lange, Jan Gustafsson and Pedro Fardim
10.1 Introduction 248
10.2 Bio-Based Foams 249
10.2.1 Starch-Based Foams 250
10.2.2 Foams Based on Vegetable Oils 253
10.2.3 Foams Based on Poly(Lactic Acid) 255
10.3 Surface Engineering of Cellulose Fibres Used in Foams 256
10.3.1 Chemical Modifications of Cellulose Fibres 257
10.3.2 In Situ Synthesis of Hybrid Fibres 258
10.3.2.1 Topology and Particle Content on Hybrid Fibres 260
10.3.2.2 Foam Formation 262
10.3.2.3 Combustion Behavior of Foams 262
10.4 Prospects 265
10.5 Summary 266
Acknowledgements 267
References 267
11 Fire Retardants from Renewable Resources 275 Zhiyu Xia, Weeradech Kiratitanavit, Shiran Yu, Jayant Kumar, Ravi Mosurkal and Ramaswamy Nagarajan
11.1 Introduction 276
11.2 Fire Retardant Additives Based on Phosphorus and Nitrogen from Renewable Resources 278
11.2.1 Nucleic Acids 279
11.2.2 Proteins Containing Phosphorus and Sulfur 286
11.2.3 Phosphorus/Nitrogen-Rich Carbohydrates 289
11.2.4 Carbohydrates 291
11.3 Natural Phenolic Compounds as Flame Retardant Additives 295
11.3.1 Lignin 296
11.3.2 Tannins 300
11.3.3 Cardanol and Polymers of Cardanol 306
11.3.4 Polydopamines 307
11.4 Other FR Materials from Renewable Sources 308
11.4.1 Chicken Eggshell 308
11.4.2 Banana Pseudostem Sap 308
11.5 Prospects 310
11.6 Summary 311
11.7 Acknowledgements 312
References 312
12 Green Composites with Excellent Barrier Properties 321 Arvind Gupta, Akhilesh Kumar Pal, Rahul Patwa, Prodyut Dhar and Vimal Katiyar
12.1 Introduction 321
12.2 Biodegradable Polymers: Classifications and Challenges 323
12.2.1 Poly (lactic acid): Properties Evaluation, Modifications and its Applications 328
12.2.2 Cellulose Based Composites: Chemical Modifications, Property Evaluation, and Applications. 333
12.2.3 Chitosan Based Composites: Chemical Modifications, Properties Evaluation, and Applications 338
12.2.4 Natural Gum Based Composites: Chemical Modification, Property Evaluation and Applications 343
12.2.5 Silk Based Composites: Property Evaluation, Chemical Modifications and Applications 348
12.3 Summary 355
Acknowledgements 355
References 356
13 Nanocellulose-Based Composites in Biomedical Applications 369 M. Osorio, A. Cañas, R. Zuluaga, P. Gañán, I. Ortiz and C. Castro
13.1 Introduction 370
13.2 Nanocellulose Sources and Properties 370
13.2.1 Nanocellulose Sources 370
13.2.2 Nanocellulose Characteristics as Green Material 373
13.2.3 Nanocellulose Properties for Biomedical Composites 374
13.2.3.1 Mechanical Properties 374
13.2.3.2 Morphology 375
13.2.3.3 Surface Charge 375
13.2.3.4 Conformability 378
13.2.3.5 Thermal Properties 378
13.2.3.6 Non-Toxic 379
13.2.3.7 Biocompatibility 379
13.3 Biomedical Applications of Nanocellulose-Based Composites 379
13.3.1 Nanocellulose-Based Composites with Various Polymers 380
13.3.1.1 Polyvinyl Alcohol 380
13.3.1.2 Chitosan (Ch) 381
13.3.1.3 Acrylic Acid (AA) 382
13.3.1.4 Polyhydroxyalkanoates (PHAs) 382
13.3.1.5 Silk Fibroin 383
13.3.1.6 Polyaniline and Polypyrrole 383
13.3.1.7 Alginate 384
13.3.1.8 Collagen 384
13.3.2 Nanocellulose-Based Composites with Bioactive Ceramics 385
13.3.2.1 Hydroxyapatite (HA) 385
13.3.2.2 Iron Oxide Nanoparticles 385
13.3.2.3 Calcium Peroxide (CaO2) 386
13.3.2.4 Carbon Nanotubes 386
13.3.3 Nanocellulose-Based Composites with Metals 386
13.3.3.1 Silver Nanoparticles (Ag) 386
13.3.3.2 Gold Nanoparticles (Au) 387
13.4 Summary 387
13.5 Prospects 390
Acknowledgments 390
References 390
Index 403
